Production of high octane gasoline



E. Jv HOUDRY June 8, 1937.

PRODUCTION 0F HIGH OCTANE GASOLINE Filed sept. 16, 1953 Pkw M/NRJ? Bf'zgme 0 y.

ATTORNEY 'Patented June 8, 1937 UNITED STATES PATENT OFFICE i 2,032,801- l i PRODUCTION F OCTANE GASOLINE AEugene J. yHouilry, Woodbury, N. J., assignor toA Houdry Process Corporation, Dover, Del., a corporation of Delaware Application September 16, 1933, Serial No. 689,695

Claims. (Cl. 196-52) 'This invention relates to the production of desirable marketable hydrocarbon products, such as benzine, gasoline, naphtha, kerosene, and the 55 down the clean 'residual oil product, and passes the lighter hydrocarbons. Since the transforming operations in the first zone take place at low pressure, the charging pump for the crude malike. More particularly it has to do with the terial supplies the pressure for this entire zone.

5 production of motor fuel of'high ,quality and The 'second zone is established immediately 5 Y high anti-knock rating, .especially in a once after the said fractionating tower, and a suitable through operation, from crude starting material, vapor pump is provided capable of imposing the wherein the only other liquid product is a clean required pressure in the outlet line. 'I'he second residual oil in the boiling range of gas oil and zone provides for absorption of the gasoline from suitable for use as Diesel oil, domestic fuel oil, the rich gases, the refining of condensed light lo or as charging stock for further conversion. In hydrocarbons along with the wild gasoline vapors certain respects the invention may be considered from the absorption step, and the stabilizingof as a further development of or improvement upon the light products after cutting the same to the my `copendlng applications, Serial Nos. 674,129 desired end point. The -high quality completely l5 and 687,553 filed on June 3, 1933, and August refined and stabilized motor fuel or gasoline is 15 31, 1933, respectively, the final product oi' the second zone. The other One object isv to effect an improved once liquid product, clean residual or Diesel oil, is through operation from crude starting material recovered in liquid form from the bottom of the without internalrecyclingand without separafractionating tower at' the 'end of the first-zone tion of intermediate products so as to produce di- With some additions from the end Point fraction- 20 rectly. only the two low and high boiling liquids ator of the second zone. referred to above and lean gas. Another object The single view in the accompanying drawing is to simplify the regulation of pressure condiindicates in a diagrammatic manner the operations throughout the system. Another object is tion of the process of the Present invention and to provide .for nexibiiity of control so that a. a preferred arrangement of apparatus for prae- 25 maximum yield of desirable high and low boiling tising the same. products may be secured from any crude starting The i'ude 011 01' other Suitable Starting ma- `material Other objects wlllbe apparent from teliel passes by line l to pump 3 which forces i the detailed description which fonows. the ssmeihrough e vsporizins yor topping stm 4 3o The invention contempistes a once through which discharges its vapors into a lorieV fraoao system mde up of two pressure Zones, In the tionating tower 5 controlled by a cooling coil 5a. I ilrst zone all of the transforming reactions take Pump 3 iS utilized t0 impose Pressure adequate to place by which conversion into light products is pessthe starting material entirely through the effected The 4gegund zone takes care of the rerst or transforming zone, where the transformiining sndstabiiising of the iight products. Each ins Operations take place at pressures normally 35 zone can be operated independently of the other, from atmospheric up. to 20 pounds per square but' they are preferably joined together to form inch. Usually a pressure of thirtypounds per a complete system for the 'conversion of' crude Square inch in fractionator 5 is enough, but, starting material. All transforming, refining and under special circumstances, it may be increased,

40 polymerizing -operations are effected with or as to sixty pounds, to take care of the back pres- .40

` upon contact masses capable of performing the K sures in the heating coils-which follow. A numdesired reactions and preferably arranged in' ber of cuts are taken from fractionator 5, such pairs or multiples thereoftoprovidefor regenera.- as an overhead cut through valved line B, or tion in place so that the process may be continuvalved line la to storage, a heavy 'naphtha cut ous with each reaction case alternately on stream through valved line 1, a middle or deep out in 45 .and in regeneration. In the first orftransformthe gas oil boiling range through line 8, and a ing zone, provision is made for reforming the residuum or bottom cut through valved outlet 9. heavy naphtha and straight run gasoline from Each fraction is arranged to be transformed, the crude topping still so as to improve the preferably by catalytic action at low or atmosoctane rating of these hydrocarbons, for transpheric pressure, so as to produce desirable motor 50 forming a middle or deep cut, and for vaporizing fuels in both the low and high boiling ranges, and transforming the bottoms. The products especially a gasoline of high octane rating.

from all these transforming operations discharge The heavy naphtha cut in line 1, with or with.. into the same fractionating tower, which throws out the overhead vapor cut in line 8, is conducted through heater Il, where its temperature i; 55

raised to the range of 800 to 950 F. and passed by line |I and suitable 'valved' connections into a series of catalytic reforming chambers 2, arranged in pairs or multiples thereof for alternate operation on stream and in regeneration. 'I'hese chambers contain suitable catalytic material for reforming the light hydrocarbon vapors to improve their octane rating, which may consist of inert, porous .materiaL such as china clay or pumice stone, or of activated hydrosilicate of alumina, preferably in molded form and containing oxides of one or more of the following metals: vanadium, chromium, tungsten, and -molybde num. The reformed vapors leave cases i2 by valved connections to line I3.

The middle or deep cut is conducted by line 8 through heater coil I4, where the temperature is raised to the range of 750 to 950o F., and thence by line |5 having valved connections to a series of catalytic transformers I8 arranged in pairs or multiples thereof for alternate operation on stream and in regeneration. These cases contain suitable catalytic adsorptive material capable of eii'ecting the desired transformation, such as molded pieces of activated 'hydrosilicate of alumina.A 'I'he products of the transformation leave cases I6 through suitable valved connections to a line i1.

The bottoms from tower 5 are conducted by line 9, together with superheated steam in suitable amount admitted by valved branch line IB, into a series of contact vaporizers I9 arrangedin pairs or multiples thereof for alternate operation on stream and in regeneration. These vaporizers may be of the type disclosed in United States Patent No. 1,806,997, issued to Alfred Joseph on May 26, 1931, but are preferably of the improved type-and arrangement disclosed in my copending application, Serial No. 670,954, led May 13, 1933 which issued February 5, 1935, as Patent No. 1,989,927. 'Ihese `chambers contain suitable inert,

porous contact masses, such as broken fragments of brick, pieces of pumice, molded units of china clay, or preferably the inert carrier material disclosed in United States Patent No. 1,818,403, issued to Alfred Joseph on August 11, 1931. The vaporized products leave ychambers I3 through suitable valved connections to line 20, which conducts them through valved connections into a series of catalytictransforming chambers 2| arranged in pairs or multiples thereof for alternate operation on stream and in regeneration, and conforming in all respects to catalytic chambers I6 and containing the same contact material.I The transformed vapors leave by suitable valved connections to line 2|a and thence by line 22 which joins with lines |1 and I3 so that all the transformed vapors are discharged by connec-` tion 22 into fractionating `tower 23, which may be controlled by a cooling vcoil 23a. Tower 23 makes a separation of the high boiling hydrocar- ,bons in the form of clean residual oil suitable for use as Diesel fuel, which leaves the bottom of fractionator 23 by a. valved line 24,- and is conducted to storage. 'I'he low boiling hydrocarbon vapors and gases leave fractionator 23 by an overhead line 25 and pass beyond the first zone,

the division between the two zones` being indicated by the broken line a.

Overhead line 25 leads to a pump 26, which marks the beginning of the second zone and im- Doses a pressure not exceeding 100 pounds per squar inch, and normally about 60 pounds per .square inch. The vapors now under pressure pass through a' condenser 21 and thence into a separator 28,`tl1e condensate leaving by-yalved line 23. while the rich gases pass by line into an absorber 3| of any suitefe or desired type.,

The absorber shown utilizes v liquid absorbent, which leaves the bottom of unit 3| in a rich con-` ditionI and is conducted by line 32 into still 33, where the wild gasoline vapors are driven off and leave by valved line 34. A The lean absorbent liquid is forced from the .bottom of still 33 through line 35 b y a suitable pump or circulator (not shown) through a cooler 36, and thence into the top of absorber 3l. y'I'he lean gases leave the top of the absorber by valved line 31.

The light hydrocarbon condensate in line 2B, and the wild gasoline vapors in line 34, are conducted together by a line 33 through a heater coil 39, where the temperature is raised to the range of 500 to 700 F., and discharged into line 40 having valved connections to a` series of catalytic refining cases 4| arranged in pairs or multiples thereof for alternate operation on lstream and in regeneration. These chambers contain suitable adsorptive. catalytic ymaterial adapted to purify and refine the light hydrocarbons and to polymerize the unsaturated components separated from the fixed gases, preferably comprising molded pieces of activated hydrosilicate of alumina containing small amounts of metallic oxides, suoliV Diesel type motor fuel from fractionator 23.

The overhead vapors passing control coil 43a are conducted by a line 45 through condenser 46 into a separator 41, whence water is withdrawn through a valved` line 4B. 'I'he hydrocarbon liquids, vapors, and gases are withdrawn from the upper part of separator 41 by aline 49 which leads to a heater coil 50, whence the hydrocar-v bons are conducted by line 5| into a stabilizer 52.

'I'he lean gases escape from the top of the stabilizer through a valved line 53,` while the refined and stabilized light end point hydrocarbons or gasoline are withdrawn by valved line 54 and conducted through a. cooler 55 and thence to storage.

As indicated above, the catalytic `reforming chambers I2, the catalytic transforming chambers i5 and 2|, the contact vaporizing chambers I9, and the catalytic refining chambers 4| are provided in pairs or multiples thereof, to permit continuous operation of the system, and are arranged for regeneration in place by known means.

The regeneration' is preferably effected by oxidation, so that all tarry and coky or sulphurous deposits left in any of the contact masses may be entirely eliminated during the regenerating periods. The regenerating medium may be air, diluted as required by flue gas or steam, but all indications of regenerating apparatus are omitted in order to simplify the drawing.

Since the catalytic transforming chambers 2| following the contact vaporizers I9 are the same as catalytic transformers I6 and contain the same catalytic material, transforming cases 2| may be omitted and the vapors, conducted lby line '20 directly into line 5, as indicated in my aforesaid copending application Serial No. 687,553. Such a simplified arrangement may be highly desirable conditions in the transforming cases 2i, as compared with transforming cases I6, Vif a maximum transformation into light products' of high quality is to be obtained from both fractions. Since the drawing is diagrammatic in character, other apparatus, including heat exchangers, coolers, etc. not essential to the understanding of the invention, are also omitted.

If desired, the application of pressure in the second zone may be deferred until after the separator 2! by the use of a liquid pump in line 29 and of a gas pump in line 30. Such anarrangement is within the spirit of the invention, but involves the use oi' two pumps instead of one, as in the form shown, vand has the additional disadvantage that condensing of the overhead from fractionator 2l is not effected under pressure.

From the above it will be apparent that the present invention' permits the grouping of all cracking and treating apparatus around a skimming or topping unit without requiring any tanks for the storage of intermediate products. This means compactness of plant, simplicity of equip'- ment, smaller investment and operating costs, and a reduced staff of operators. By arranging the apparatus in denite pressure zones, pumping equipment is much reduced without any sacrice of eiciency or of flexibility of operation.

I claim as my invention: y

l. Process for the production of high quality motor fuel in a once through operation from crude hydrocarbon starting material which comprises vaporizing the starting material, fractionally condensing the vapors into a plurality of cuts, heating and transforming the cuts individually but simultaneously by contacting the same at reaction temperature with beds of catalytic material capable of effecting the desired transformation and of producing cleanproducts, combining the products of the transforming reactions, fractionating the combined products to separate out and withdraw as afinished product a liquid fraction in the form of a clean motor fuel oil of the Diesel type, subjecting the overhead vapors from the last fractionating zone to pressure, condensing the compressed vapors and separating the same into condensate and uncondensed material, separating the uncondensed material into light hydrocarbons and lean gas, removing the lean gas, combining the light hydrocarbons and the condensate and passing the same together through a heating and vaporizing zone, subjecting the heated and vaporized material to the action of a bed of catalytic material capable of refining and polymerizing the same, fraction ating the refined material to remove liquid polymers outside the gasoline boiling range, and removing entrained gases from the4 remaining -ma-` terial to produce a second motor fuel in the form of finished end-point gasoline.

2. In the productionof high quality motor fuels in a continuous once through operation from crude hydrocarbon starting material, the operating process which comprises imposing a pressure on the starting material. distilling and fractionating the starting material under a pressure of approximately 30 pounds per square inch, separately vaporizing ad separately transforming all ofthe fractions in .vapor phase in the 3 temperamre range of 75o to 950 F. by the action of catalytic masses comprising essentially blends of silica and alumina having selective adsorptive properties and capable of producing clean products, combining the products of the transforming operations and fractionating the same to separate out a single liquid or bottom fraction which is clean finished motor fuel oil of the Diesel type, continuously passing the overhead fraction from the last fractionating step into a second zone under an-increased pressure of theorder of 60 pounds per square inch, condensing the compressed vapors to pro'duce condensate and light hydrocarbons and gases, separating the said light hydrocarbons from the gases, combining the said light hydrocarbons with the condensate and subjecting them to a heating and vaporizing step, catalytically refining the resulting materialin vapor phase inthe temperature range of 500 to 700 F. by the action of a catalytic mass comprising essentially a. blend of silica and alumina with other metallic compounds having selectlve adsorptive properties, fractionating the refined material to remove a liquid fraction which ls clean and which is added to the Diesel type motor fuel, and stabilizing the overhead products of the llast named fractionating step bythe removal of entrained gases to obtain a lsecond motor fuel in the form of ni-shed and stabilized end-point gasoline.

3.' In the production of yhigh quality motor fuels in a continuous once through operation from crude `hydrocarbon starting material, the operating process which comprises heating and at least partly vaporizingV the starting material under pressure in a primary transforming zone, fractionating the heated and vaporlzed material into an overhead cut, a heavy naphtha cut, a gas oil cut and abottom cut, reforming the heavy naphtha cut with or without the overhead cut in vapor phase by the action of an adsorptive contact mass containing metallic Ipxides from the group containing vanadium" chromium,

.tungsten and molybdenum, revaporizing and drosilicate of alumina, effecting the aforesaid operations separately but simultaneously and at pressures derived from said heating and fractionating steps, fractionating together lall the products of all the aforesaid operations to separate out as a nished product a single liquid fraction which; is a clean motor fuel oil of the Diesel type, continuously passing the overhead fraction from the last fractionating step into a second zone and subjecting it to a higher pressure than in said primary transforming zone which pressure continues substantially throughout the rest of'the process, subjecting the last named overhead fraction to condensation to produce condensate and uncondensed lighter material, removing from said lighter material by an absorption operation the lean gas tov leave certain desirablefl light hydrocarbons, combining said desirable light hydrocarbons with the aforesaid condensate and subjecting them 'together to a heating and vaporizing operation, subjecting the vaporized and heated material in the temperature range of 590 to 709 F. to the action of a refining catalyst comprising essentially activated hydrosilicate of alumina, fractionating the products to remove ay heavier liquid fraction which is added to the aforesaid Diesel type motor fuel and to secure a desired end-point overhead material, and subjecting .the last named overhead material to a stabilizing operation involving the removal of entrained light gases thereby to produce a second. motor fuel in the form of finished stable end-point gasoline of desirable lantiknocl:

quality.

, 4. Apparatus for the production of lhigh quality motor fuel in a once through operation from crude hydrocarbon starting material comprising a Avaporizing or topping still into which the crude starting material is fed, a fractionator for the vapors from said still, means withdrawing material from said fractionator in aplurality of cuts, a plurality of heating means and catalytic cases for transforming each of said cuts individually but simultaneously, a single fractionator.

intoV Which all of the transformed material from said cases is discharged, an outlet from the lower part of said last named fractionator for withdrawing as al finished product a liquid fraction in the form of a clean motor fuel oil of the Diesel type, an outlet line from the upper part-of said .last named fractionator for the overhead 'material, a pump in said line for imposing on said vapors a pressure sufficient to force the latter through the remainder of the apparatus, condensing and separating means into which said vapors are forced by said pump, means for lseparating the uncondensed material into light hydrocarbons and lean gas, a heater for vaporizing the condensate receiving the latter `and said light hydrocarbons, refining cases containing catalytic masses receiving the vaporized condensate and heated light hydrocarbon mixture, a fractionator receiving the products of -said cases, and means for removing entrainedgasesfrom the overhead fraction from' said fractionator to produce a second motor fuel in the form of finished end point gasoline.

5. `Apparatus: for the lproduction of high quality motor fuel ina once through operation from `crude hydrocarbon starting material arranged in two pressure zones, theA first zone comprising a feed line having a liquid pump therein', a topping still into which said line and said pump discharge,

va fractionator connected to the outlet of said topping still, lines extending from various. levels of said fractionator for withdrawing therefrom a plurality of cuts, a heater and at least one cata-- lytic transformer in each of said last named lines, a second fractionator connected to all of said catalytic transformers to receive the transformed material therefrom and for'separating it into a single liquid fraction which is a high boilcarbons from the fixed gases, a heater, meansA conducting the condensate from said separator and the light hydrocarbons from said absorbing means to said heater, a catalytic refining case connected to said heater to receive the heated and vaporized condensate and light hydrocarbons, an end point fractionator connected to said case to receive the refined products thereof, a discharge line from the upper end of said end point fractionatorfand a stabilizing means in said last named line for the overhead vapors for removing'entrained fixed 'gases therefrom sofasto produce a. second motor fuel in the form of finished end point gasoline.v

EUGENE J. HOUDRY.

` CERTIFICATE 'or CORRECTION.

'Patent No. 2,082,801.

EUGENE J. Hounar.

v It is hereby certified that' error appears in the printed specification 1.;of.tlief above numbered patent. requiring correction as follows: .Pageli lsecond column, line 43,Y claim 3, for the word "containing" read comprisi fg; and ythat the said Letters Patent should be read with this correction. therein that the same may conform to the record of the case. .in the Patent office.y f .i

'I Signed and sealed this 24th yday of August, A. D. 1937.

"Leslie Frazer `Acting rCommissioner of Patents.

1' (Seal) refining catalyst comprising essentially activated hydrosilicate of alumina, fractionating the products to remove ay heavier liquid fraction which is added to the aforesaid Diesel type motor fuel and to secure a desired end-point overhead material, and subjecting .the last named overhead material to a stabilizing operation involving the removal of entrained light gases thereby to produce a second. motor fuel in the form of finished stable end-point gasoline of desirable lantiknocl:

quality.

, 4. Apparatus for the production of lhigh quality motor fuel in a once through operation from crude hydrocarbon starting material comprising a Avaporizing or topping still into which the crude starting material is fed, a fractionator for the vapors from said still, means withdrawing material from said fractionator in aplurality of cuts, a plurality of heating means and catalytic cases for transforming each of said cuts individually but simultaneously, a single fractionator.

intoV Which all of the transformed material from said cases is discharged, an outlet from the lower part of said last named fractionator for withdrawing as al finished product a liquid fraction in the form of a clean motor fuel oil of the Diesel type, an outlet line from the upper part-of said .last named fractionator for the overhead 'material, a pump in said line for imposing on said vapors a pressure sufficient to force the latter through the remainder of the apparatus, condensing and separating means into which said vapors are forced by said pump, means for lseparating the uncondensed material into light hydrocarbons and lean gas, a heater for vaporizing the condensate receiving the latter `and said light hydrocarbons, refining cases containing catalytic masses receiving the vaporized condensate and heated light hydrocarbon mixture, a fractionator receiving the products of -said cases, and means for removing entrainedgasesfrom the overhead fraction from' said fractionator to produce a second motor fuel in the form of finished end point gasoline.

5. `Apparatus: for the lproduction of high quality motor fuel ina once through operation from `crude hydrocarbon starting material arranged in two pressure zones, theA first zone comprising a feed line having a liquid pump therein', a topping still into which said line and said pump discharge,

va fractionator connected to the outlet of said topping still, lines extending from various. levels of said fractionator for withdrawing therefrom a plurality of cuts, a heater and at least one cata-- lytic transformer in each of said last named lines, a second fractionator connected to all of said catalytic transformers to receive the transformed material therefrom and for'separating it into a single liquid fraction which is a high boilcarbons from the fixed gases, a heater, meansA conducting the condensate from said separator and the light hydrocarbons from said absorbing means to said heater, a catalytic refining case connected to said heater to receive the heated and vaporized condensate and light hydrocarbons, an end point fractionator connected to said case to receive the refined products thereof, a discharge line from the upper end of said end point fractionatorfand a stabilizing means in said last named line for the overhead vapors for removing'entrained fixed 'gases therefrom sofasto produce a. second motor fuel in the form of finished end point gasoline.v

EUGENE J. HOUDRY.

` CERTIFICATE 'or CORRECTION.

'Patent No. 2,082,801.

EUGENE J. Hounar.

v It is hereby certified that' error appears in the printed specification 1.;of.tlief above numbered patent. requiring correction as follows: .Pageli lsecond column, line 43,Y claim 3, for the word "containing" read comprisi fg; and ythat the said Letters Patent should be read with this correction. therein that the same may conform to the record of the case. .in the Patent office.y f .i

'I Signed and sealed this 24th yday of August, A. D. 1937.

"Leslie Frazer `Acting rCommissioner of Patents.

1' (Seal) 

